Hf alkylation of hydrocarbons in the presence of tempering agents



ISOF'ARAFF'iN RECYCLE Feb. 18, 1947. FREY 2 ,416,000

HF A LKYLA'ITION OF HYDRQ'ZMR BQNS IN THE PRESENCE OF TEMPERING AGENTS I 'Filed July 17, 1944 2 Sheets-Sheet 1 uowuousyaa Fla.

HOLVNOIJDVUJ WATER HF BQLVUVdBS HOLVUVdBS ALKYLATOR BOLVHVdBS INVENTOR FREDERICK E. FREY' ATTOR EYS F. E. FREY Feb. .13, 1947.

HP ALKYLATION OFHYDROCARBONS IN THE PRESENCE OF TEMPERING AGENTS 2 Sheets-$het 2 uzsbm Filed July 17, 1944 HOLVHVdBS HOLVNOLLQVHJ INVENTOR FREDERICK E FREY ATTORm Z VHOLVNOILQVHJ now ouovaa UOLVHVdBS aerator;

. ALKYLATHGN 01F RARBQNS THE ERESENCE 0F 'EEMPERENG AGENTS Frederick E. Frey,

=rtlesvllle, Okla, assignor to Phillips Petrole Company, a corporation of Delaware Application .iuly 1'1, 19%, Serial No. 545,309 I able tempering agents, for effecting catalytic alkylation of alkylatable hydrocarbons, especially isoparamnic and aromatic hydrocarbons. This application is a continuation-in-part of my copending' application Serial No. 450,588, filed July 11,1942, now U. S. Patent 2,384,294, granted September 4, 1945.

' In a typical method of conducting an alkylation reaction, an alkylatable hydrocarbon is agitated with-substantially anhydrous hydrofluoric acid to produce a liquid mixture or emulsion which is maintained at a reaction-temperature suitable for alkylation, and an alkylating reactant is introduced in such a way as to maintain only a very low concentration of alkylating reactant in the mixture. After a suitable reaction time the hydrocarbon layer may be decanted, and the juncture product or alkylate maybe separated from the other hydrocarbons, as by fractional distillation. This reaction can be efiected not only at temperatures requiring some degree of refrigeration, that is, below room temperature, as is the commercial practice when sulfuric acid is used as an alkylating catalyst, but also at tem- 12 Claims- (ci. cameras) uct is desired, this scission produces an undeperatures equal to and above ordinary temperatures, whereby the need for refrigeration is avoided. Hydrogen fluoride lacks the oxidizing tendency which sulfuric acid possesses and which leads to the formation of sulfur dioxide and sludge compounds in serious degree when the latter catalyst is used'for alkylatlon at elevated temperatures. The alkylation reaction is exceedingly rapid at the higher temperatures; for example, it can be virtually completed in less than three minutes at 125 F. when using butylenes and isobutane as reactants with hydrogen fluoride as the catalyst. At such an elevated reaction temperature, however, as compared with the result obtained at, for example, a temperature lower by 50 F., the actual and/or efiective' scission of the primary juncture product becomes quite marked, butylenes plus isobutane yielding, for example, not only iso-octane, which preponderates at the lower reaction temperature, but also considerable pentanes,. hexanes, and hep-- tanes. When, from the standpoint of volatility or-antiknock quality, the primary juncture prodsirable loss in quality of the product.

In a modified hydrofluoric acid alkylation process, such as that disclosed in my copending ap= plication, Serial No. 429,962, filed February 7, 1942, now U. S. Patent 2,384,735, granted September 11, 1945, olefins are absorbed from a hy-- drocarbon stream by liquid concentrated hydrofluoric acid, and the resulting mixture is used to alkylate a suitable alkylatable parafiln. Be-

cause of the'tendency of oleflns to polymerize in concentrated hydrofluoric acid, the temperature of the acid-olefin mixture must be relatively low, preferably below room temperature, and/or the period of time elapsing between the absorption step and the alkylation step must be very short, and/or the hydrofluoric acld-to-olefln ratio must be relatively high, for example, above 10:1.

An object of my invention is to increase the yield of primary products in a hydrofluoric acid alkylation process.

Another object is to inhibit the formation of low-boiling hydrocarbons in hydrofluoric acid alkylation products.

A. further object is to reduce or eliminate the need'for refrigeration in producing a product of given characteristics and quality.

A further object is to increase the stability of v oleflns in concentrated hydrofluoric acid, partic ularly against polymerization.

Another object is to decrease the rate of forreaction mixture, or to reactants in limited pro-v portions to temper the activity of the catalyst and to inhibit deleterious side reactions. Fur

ther, I have found that oleflns, when dissolved in hydrofluoric acid containing such a tempering agent, retain their usefulness as alkylating agents for'longer times than when a tempering agent is not present. Still further, I have found that most of these agents may be advantageously recovered and recycled to the process.

In accordance with my that the additive agents exerting this tempering effect are polar compounds which are preferentially soluble in the hydrofluoric acid phase of alkylation reaction mixtures and which have a definite or potential basicityor attraction for the hydrofluoric -acid due to the presence in the molecule of the tempering agent of a basic nitrogen atom or a. hydroxyl group as exemplified by the following types of compounds: ((1) compounds containing a basic nitrogen atom such as ammonium compounds including ammonia, amino, amido,-imino and imido compounds, the class of compounds being further exemplified by acid amides, such as acetamide, aliphatic amines, such as the butyl amines and ethylene diamine, and other aliphatic and cyclic nitrogen compounds including organic bases, such as quinoline, aniline, naphthylamines, toluidine, hexamethylene tetramine, pyridine, piperidine, toluylene diamlne, inorganic ammonium compounds such as ammonium fluoride and the like may be used also; (b) hydroxylated organic compounds including aliphatic and aromatic alcohols such as methanol, ethanol, alcohol amines such as ethyanolamine, phenol, catechol and other polyhydric phenols, and organic acids such as acetic, benzoic, tartaric, etc. Secondary or tertiary alcohols, while also operative, are not as desirable because of their tendency to form olefins by dehydration, however.-

It will thus be seen-that,the compounds which may be utilized as temperingagents are those invention I have found which are relatively basic to hydrofluoric acid increases the interfacial surface area which is obtainable by mechanical agitating devices, and thus facilitates the transfer of the alkylatable hydrocarbon into, and of the primary product out of, the acid phase. Most tempering agents also change the electrical conductivity and/or the dielectric constant of concentrated liquid hydrofluoric acid and therefore presumably aflect the dissociating and/0r ionizing power of the acid. Practically, the effect may be described as a reduction of the action of the acid on freshly formed primary alkylate, and in some instances, retardation of therate of reaction of oleflns in the acid, thereby reducing the extent of side reactions, such as polymerization and cyclization, and decreasing the formation of acid-soluble materials,"

The tempering agents, such as have been de- 3 scribed, may be dissolved in the hydrogen fluoride phase, andthe alkylation of isoparaflln with an olefin or other alkylating reactant may then be '.conducted in any of the conventional ways wherein the hydrocarbon reactants are brought into contact with the catalyst in the liquid state. Suitableconcentrations of the tempering agents are usually: n the range of about 0.1 to 10 per cent.

by weight of the acid. though in many instances this range may be exceeded without pass g be- 4 yond the scope of this invention; the optimum concentration may be readily determined by trial in any particular instance..

Understanding of my invention may be aided by the accompanying drawings in which Figure 1 is a schematic flow-diagram of one arrangement for practicing this invention in a hydrofluoric acid alkylation process, and Figure 2 is a schematic flow-diagram of an arrangement for practicing this invention in a modified process wherein olefins are first absorbed in concentrated hydrorluoric acid containing an addition agent and the resulting mixture is used to alkylate a suitable alkylatable hydrocarbon.

In Figure 1 a suitable addition or tempering agent, for example quinoline, aniline, pyridine, or ammonia (as such or as an ammonium compound such as ammonium fluoride or bifluoride), is admitted to the system through inlet ll having valve I2 to mixer l3, wherein it becomes dissolved in liquid concentrated hydrofluoric acid, which may be admitted through inlet I! having valve 15. Mixer 13 may be very simple; usually, simply injecting the modifying agent into a conduit which carries hydrofluoric acid will sufllce as a means of mixing. The proportion of tempering agent may be from about 0.01 to about 20 per cent by weight of the hydrofluoric acid. The optimum concentration depends upon the particular agent used and upon the operating conditions; usually it is in the range from about 0.1 to 10 per cent by weight of the hydrofluoric acid, and it may be readily determined by trial in any particular instance.

The eiiluent from mixer l 3 passes through valve I 6 and conduit H to alkylator 26, wherein it is agitated with a mixture 'of an alkylatable hydrocarbon and an alkylating reactant in suitable proportions. This mixture, which may be, for example, an isoparaflin, such as isobutane or isopentane, and an olefin, such as propylene or butylcne, may be admitted through one or more inlets, such as inlet 2'! controlled by valve 28. The alkylating conditions usually may be as follows: temperature, 50 to 200 F.; pressure. sufliclent to maintain all components in the liquid phase; contact or time or residence in alkylator 28, 1 to 30 minutes; vigorous agitation; and, preferably, maintenance of a large excess of the alkylatable hydrocarbon over the alkylating reactant.

The resulting mixture from alkylator 26 is passed through valve 45 and conduit 46 to separator 41, wherein it is separated into two liquid phases, as by cooling and/or gravitational or centrifugal means.

The lighter or hydrocarbon phase is passed through conduit 48 having valve 49 to fractionator 50, wherein it is separated into the following five fractions: (1) A very minor fraction comprising non-condensable gases, which may be withdrawn through outlet Blhaving valve 52; (2) a fraction comprising low-boiling alkylatable saturated hydrocarbon material, which may be recycled via conduit 56 having valve 51 to alkylator 26; (3) a fraction comprising excess low-boilingalkylatable hydrocarbon and/or relatively difficultly alkylatable low-boiling hydrocarbons. which may be removed from the system through outlet 58 having valve 59; (4) a fraction comprising highly branched parafiinic hydrocarbons suitabl for use in motor fuel, which may be withdrawn through outlet 60 having valve GI; and (5) a relatively small and high-boiling hydrocarbon fraction, which may be withdrawn through outlet 62 having valve 63.

The heavier or hydrofluoric acid phase from separator 41 may be recycled through valve 85 and conduit 66 to the acid inlet I4. Preferably, however, at least part of it is passed through valve 69 to acid fractionator 10, wherein it is separated into two fractions. An overhead fraction comprising substantially pure anhydrous hydrogen fluoride and lesser proportions of relatively lowboiling hydrocarbons is passed through valve II and conduit 12 to separator 55. A bottom fraction, which comprises mainlyacid-soluble hydrocarbons, fluoro-organic material, hydrogen fluoride, some incidentally introduced water, and the tempering agent, is passed through valve 74 and conduit 15 to separator IS.

A stream of water is injected into conduit 15 through valve 80 and inlet 8! and is mixed therein with the acid sludge or residue from fractionator 10. The water extracts hydrogen fluoride and tempering agent from the'acid sludge. The carbonaceous materials are substantially insoluble and separate out in separator-l6 as an oily layer, which is removed through outlet 82 having valve 83.

The aqueous phase is passed fromseparator 16 through conduit 85 and valve 86 to a fractionator 81, wherefrom water and'hydrogen fluoride are withdrawn overhead through valve 80 and outlet 99, and the recovered tempering agent is withdrawn as a bottom product in condition suitable for recycling to inlet "I l, as through valve 92 and conduit 93. If desired, part or all of the aqueous overhead fraction from fractionator 81 may be recycled through valve 90 and conduit 9| to conduit I5 for re-use as extracting fluid.

The above-described flow-scheme is suitable for use with tempering agents or their compounds with hydrofluoric acid which are soluble in water or dilute aqueous hydrofluoric acid. This is true of many or'the preferred agents; however, some may not fall within this category and hence may requirediflzerent means of recovery for recycling.

are insoluble in water or dilute aqueous hydrogen fluoride may be extracted by some other prefer ential solvent, such as an alkaline solution. Addition agents which are dissolved inthe hydrocarbon phase or products may. be recovered sim-. ilarly by distillation or acid, alkali, or water ex traction steps (not shown in the drawings), as will be obvious to those skilled in the arts of chemistry and chemical engineering. The most 6 weight of the hydrofluoric acid; it may be readily determined by trial in any particular instance.

The effluent from mixer l3 passes through valve l8 and conduit I! to a second mixer l8, into which is admitted, through inlet l9 and valve 20, a liquid 'or liquefied hydrocarbon stream which contains oleflns. The olefins are preferably present in proportions of 1 to per cent or more by weight of the hydrocarbon'and are of the type suitable .for use as alkylating agents, for example, propylin the liquid phase; total contact time, 5 seconds to 15 minutes or more;' acid-to-olefln ratio, 5:1 to 20:1 by weight. These conditions are considerably less limited than those which I prefer to use when no inhibitor is present in the acid phase. For example, if no inhibitor is used. the preferred conditions are: temperature, 30 to 150 F.; acidto-olefln ratio, 10:1 to 50:1 byweight or more. Broadening f the ge of operating conditions and advantageously operating under what formerly were the less favorable conditions, especially oi the temperature and the acid-olefin ratio is possible in theprocess of this invention because the addition agent markedly lowers the tendency of the oleflnic material dissolved in hydrofluoric acid to undergo polymerization and/or other side reaction which adversely affect its utility as an alkylating catalyst.

The olefln-in-acid phase from centrifuge 23 is.

passed through'valve 2t and conduit 25 to alkylator 26, in which it isagitated under alkylating conditions with an alkylatable hydrocarbon, such as isobutane or isopentane, which may be introsuitable modification for recovering and recycling the tempering agents will be apparent to those skilled in the art from the foregoing discussion,

together witha consideration of the properties of the particular agent selected for use.

In Figure 2, a suitableaddition or tempering agent, for example, quinoline, aniline, pyridine, or ammonia, as previously mentioned, is admitted to the system through inlet ii and valve I2 to mixer 53, wherein it becomes dissolved in a liquid concentrated hydrofluoric acid phase which may be admitted through inlet it having valve 135.

duced through valve 2'! and conduit 28. Preferably, the proportion of alkylatable hydrocarbon to olefin is from 2: 1 to 15:1 by weight. The alkylating conditions are preferably as follows: temperature, 75 to 200 F.; pressure, sumcient, to maintain all components in the liquid phase; time, 1 to 30 minutes. Here again the operating conditions may be less favorable or less closely controlled for producing a product of given quality and yield than when no tempering agent is used; for example, if no addition agent is used; the corresponding preferred temperature range is from about 30 to F. The tempering agent apparently reducesboth the extent of side reactions and the tendency of the primary alkylation product to undergo secondary or reconstruction reactions.

The olefin-depleted hydrocarbon phase from centrifuge 23 passes through valve 20 and conduit 30 to a distributing means it in washer or absorber 32.1 The hydrocarbon rises, by virtue of its relatively low density, countercurrently to downwardly flowing hydrofluoric acid which may be introduced as the concentrated or anhydrous acid near the middle of the absorber through inlet 33, valve 3t, and distributing means 35. Dissolved organic fluorides are absorbed from the hydrocarbon phase by the hydrofluoric acid,

which, after a short settling period in space 38 ing agent and for subsequent use as olefinab sorbing liquid in mixer 98. Although as the hyrides, appreciable quantities of hydrofluoric acid remain dissolved in the hydrocarbon. The hydrocarbon continues rising in the upper half of the absorber, wherein-it is contacted with a countel-currently flowing aqueous phase, introduced as water or as a dilute solution of hydrofluoric acid of up to about 40 per cent in strength, preferably a constant-boiling mixture, through valve 88, inlet Ill, and distributing means I. The water or solution extracts the dissolved hydrofluoric acid from the hydrocarbon phase. If desired, part or all of the aqueous acid introduced near the top of absorber 32 may be withdrawn just above distributing means 85, for example, from a bubble tray or other collecting device 94. It

may be recycled through conduit 85, pump 88,

and valve 81 to distributing means Ii, or it may be passed by a means not shown on the drawings to an acid-recovery unit, such as fractionator 18. The hydrocarbon phase, after a short settling period in space 42 at the top of washer 32, wherein it is separated from the aqueous phase. is withdrawn through outlet '48 having valve 44'; if desired, this material may be passed to a fractionator, not shown, to recover isoparaflins for alkylation.

The uantity of water or aqueous dilute hydrofluoric acid introduced is preferably about onetwentieth to one-tenth of the volume of hydrocarbon treated; .a much larger proportion introduces excessive'amounts of water into the system, whereas a much smaller proportion does not effect substantially complete recovery of hydrofluoric acid from the hydrocarbon. The quantity of concentrated hydrofluoric acid introduced in the central portion of the washer preferably is from one-fourth to two times the volume of hydrocarbon treated, and should be at least flve times the volume of aqueous solution introduced at the top of the washer. Smaller amounts do not always completely remove alkyl fluorides from the hydrocarbons or are diluted too. much by the aqueous solution from the top of the washer, whereas larger amounts produce an unnecessarily high ratio of acid to hydrocarbon in alkylator 28.

' The reaction product from alkylator 28 passes through valve 45 and conduit 45 to separator 81, wherein it is separated into two liquid phases,

as by cooling and/or gravitational or centrifugal means.

Of these phases, the lighter or hydrocarbon phase is passed byway of conduit 88 having valve 48 to fractionation unit 50, in which it is sepa- 'rated by fractional distillation into the following through outlet 88 having valve 5|; and (6) a high-boiling bottom fraction, comprising heavy polymers and otherby-products, which is withdrawn through outlet 82 having valve 83.

. Theheavier or hydrofluoric acid phase from separator fl'may be recycled through conduit 88, valve 85, acid recycle conduit 88 and valve 81 and/or valve 88 to absorber 82 and/or mixer i8, respectively. Preferably, however,- at least part of it is passed through valve 89 to acid fractionator 18, in which it is separated by fractional distillation into the following three fractions: (1) a minor low-boiling fraction comprisinghydrogen fluoride and low-boiling hydrocarbons, which is passed through valve II and conduit I2 to separator 55; (2) a major fraction of substantially pure hydrogen fluoride which is passed through valve 13 to acid recycle conduit 66; (3) a kettle fraction comprising water, hydrofluoric acid, tempering agent, and an organic residue, which is passed through valve 18 and conduit 15 to separator 18.

Separator 55 effects separation of the overhead azeotropes from fractionators 50 and I8 into two liquid phases, as by cooling and gravitational or centrifugal means. The lighter or hydrocarbon phase is withdrawn through outlet 11 having valve 18; the heavier or hydrofluoric acid phase is passed through valve 19 to acid recycle conduit 58.

Into the inhibitor-containing fluid in conduit 15 is injected by means of valve 80 and conduit 8| 'a selective solvent, preferably water or a dilute aqueous solution containing a suitable chemical reagent, to extract the tempering agent. Water or a dilute aqueous solution of hydrofluoric acid is usually suitable for extracting tempering agents of the basic nitrogen type: alkaline soluunreacted alkylatable hydrocarbons, such as isobutane or isopentane, which is recycled via conduit 58 andvalve 51 to alkylator 28; (4) .a fraction comprising relatively diflicultly alkylatable hydrocarbons, such as normal butane, which is withdrawn through outlet 58 having valve 58;

(5)- a substantial fraction of the desired highly branched paraflinic reaction products boiling within the gasoline range, which is withdrawn tions are usuaily'suitable for extracting phenolic or hydroxy organic agents. In separator I8 the resulting mixture from conduit 15 is separated, as by cooling and/or gravitational or centrifugal means, into two liquid phases. The lighter .or hydrocarbon phase is withdrawn through outlet 82 having valve 83. The heavier or aqueous phase, containing the tempering agent, may be recycled through valve 84 and conduit 85 to the top section of absorber 32 for use as absorbing fluid therein: preferably, however, a part of it is passed through valve 88 to fractionator 81 which separates it into two fractions. The lowerboiiing fraction-from fractionator 81 comprises mainly water or other solvent and may be withdrawn through outlet 88 having valve 88; preferably, however. part or all of it is recycled through valve and conduit 9! to conduit 15 for re-use as inhibitor-extracting fluid. The higher-boiling fraction, which comprisw substantial proportions of recovered tempering agent or simple chemical derivatives thereof, is recycled through valve 82 and conduit 83 to mixer ii. If desired, the recovered tem ering agent may be subjected to further purification steps, not shown in the drawings. before recycling.

The foregoing general flow schemes are preknown to those skilled in the art, may be supplied wherever they are necessary or convenient.

The alkylation conditions hereinbefore described are generally suitable for alkylation of readily allqlatable hydrocarbons like isoparamns and aromatics of the type of benzene or toluene with oleflns or with alkyl compounds (alcohols, halides, ethers, esters, etc.) having three or more carbon atoms in the alkyl group; however, when ethylene or an ethyl compound is used, somewhat more drastic conditions, such as higher temperatures, may be advantageously employed.

To illustrate further some of the many aspects of my invention, the following examples are given.

EXAMPIEI In a process similar to that which is embodied in Figure 2, isobutane is alkylated with mixed butylenes from a C4 refinery gas fraction. Sufflcient quinoline is added to the hydrofluoric acid used to absorb olefins to give an acid-to-quinoline ratio of 20 to 1 by weight. The operating conditions are about as follows: temperature in the olefin extractor, 105 F.; pressure in olefin extractor, 150 pounds per square inch; time of contact of olefins with hydrofluoric acid prior to the alkylation step, 6 minutes; alkylator temperature, 125 F.; alkylator pressure, 125 pounds per square inch; reaction time, minutes; hy-

. drogen fluorlde-to-olefin ratio, 10:1; isobutaneto olefin ratio, 3.5:1. Under these conditions is produced an aviation-gasoline product in high yield and of good quality.

EXAIMPLE II EXAMPLES III, IV, AND V Three batch runs, hereinafter referred to as Examples III, IV, and V, were made for alkylating isobutane with butene-l under similar conditions except for the composition of the catalyst. In Example III, the catalyst consisted of anhydrous hydrofluoric acid modified by 5.6

weight per cent of methyl alcohol; in Example IV, it consisted of anhydrous hydrofluoric acid modified by 8.0 weight per cent of glacial acetic acid; and in Example V, it consisted of unmodifled anhydrous hydrofluoric acid. An 18-liter steel reactor provided with a motor driven 540-R. P. M. stirrer wasused in each run. The catalyst and the isobutane were mixed together, and the butene-l was then added at a uniform rate. After the butene-l had been added, the stirring was continued for a short additional period; the average contact time of the hydrocarbon reaction mixture with the acid was about the same for all three runs. The mixture was allowed to separate into two layers, and the hydrocarbon layer was removed, acid-freed, debutanized, and examined. Experimental data for these three examples are given in Table I. It will be noted that the proportion of octanes in the total alkylate was higher in Example 111 than in Example V; that the yield higher in Example VI than in 10 r a of the aviation-gasoline fractions based on total debutanized alkylate was higher in Examples 111 and IV than in Example V; that the octane numbers of the aviation-gasoline fractions produced in Examples III and IV were markedly higher than in Example V; that the lead susceptibility of the aviation-gasoline fraction from Example III was slightly higher than that fromExample V; and that these favorably different octanerating effects were obtained in spite of higher cut points used for obtaining the aviation-gasoline fractions in Examples III and IV.

Team: I

HF alkylation of isobutane with butane-1 Example III IV V Catalyst modifier Methanol Acetic acid None Temperature, F 100-117 97-ll3 99-113 Pressure, s. i 78-99 82-100 93-111 Average 16 14. 5 14. 5

Isobutane/butene ratio (wt.) 12. 50 ll. 02 12. Total hydrocarbon/HF ratio (wt.) 2. l6 2. 21 2. 27

Composition; volume per cent: o

0. 2. 2 4. 4' 86. 2 0.7 0.7 3.1 7. 8 D-- Heavier 2. 7 3. 1

Totalm; 100. 0 100. 0 Aviation-gasoline fraction:

Out point, 365 367 856 Volume per cent 0'! total elk ate-.--. 95.5 97.2 91.4 A. S. l M. distillation, F-

First drop 178 128 192 10 per cent evaporated... 208 184 212 50 per cent evaporated" 218 221 221 per cent eveporeted.. 229 234 229 End point 348 364 300 Octeng/I number (A. 8. '1.

0 cc. TEL 93. 3 92. 5 89. 2 1 cc. TEL- 102. 2 07. 8

Two continuous pilot-plant runs hereter referred to as Examples VI and VII, were made 4.5 weight per cent of ammonia, added in the formof ammonium bifluoride; in Example V11 it consisted of unmodified anhydrous hydrofluoric acid.

A 1470-ml. steel reactor provided with a motordriven, l725-R.,P. M., 2.5-inch turbo-mixer was used in both runs. The hydrocarbon feed was pumped into the reactor, where it was agitated with'approximately an equal volume of hydro fiuoric acid for a desired average contact or residence time. The reaction mixture was then passed to a separator, where it separated into two layers. The acid phase was returned to the reactor by gravity. The hydrocarbon phase, which was collected in cylinders, was debutanized and examined. Experimental data for these two runs are given in Table II. It will be noted that the yield and the octane rating of the aviation gasoline fraction and of the total alkylate were Tenn: 11

HF alleviation of isobutane with butane-1 Example VI VII Ammonia, wt. per cent oi HF 4. 5 None Temperature, F 91 88 Pressure, s.i 130 130 Contact t e, min. 10.4 11.1 Isobutane utene wt.) 4. 9 4. 9 H rocar ongiF vol.) 1. 13 1.15 Y id of siky te, wt. per cent of butcne 203 192 Aviation-gasoline fraction:

$1! F "fireman- 9 93 i e ,voumeperceno o e 3. A. B. T. M. distillation, F,

First drop 158 151 10 per cent evaporated 197 204 60 per cent evaporated. 223 224 90 per cent evaporated. 254 250 End point 365 368 Gravity, A. P. I 68 6 69.0 Reid vapor pressure, lb 2 45 2. 80 A. S. 'l". M. octane number, 0 ml. TEL- 89 4 87. 4 Total alkylate:

A. 8. T. M. distillation, F First drop 127 162 10 per cent evaporated 193 203 50 per cent evaporated. 226 227 90 per cent evaporated. 317 293 End point 412 463 Gravity, A P. 67.9 67.8 Reid vapor pressure, lb 3. 60 2. 75 A. S. T. M. octane number, 0 ml. TEL 89 2 85. 3

Because the invention may be practiced otherwise than as specifically described herein, and because many modifications and variations of it will be obvious to those skilled. in the art, it should not be restricted except as specified in the appended claims.

I claim:

1. A process for alkylating relatively low-boiling 'aikylatable hydrocarbons with relatively lowboiling oleflns to produce high-boiling hydrocarbons in the presence of concentrated'hydrofluoric acid as a catalyst, which comprises admixing with said hydrofluoric acid from about 0.1 to about 10 weight per cent of a polar nitrogen compound having a basic reaction as a tempering agent, contacting the resultant liquid mixture with a hydrocarbon mixture containing low-boiling oleflns and saturated hydrocarbons to absorb said low-boiling oleflns therein, separating the olefin-free saturated hydrocarbons therefrom, introducing the liquid olefin-containing hydrofluoric acid together with the tempering agent into an alkylation zone along with a low-boiling alkylatable hydrocarbon, introducing said oleflnfree saturated hydrocarbons into an absorber in contact with concentrated liquid hydrofluoric acid to absorb organic fluorides formed during aforesaid olefln-absorption step, introducing the resultant liquid hydrofluoric acid used for contacting said saturated hydrocarbons into said alkylation zone as a portion of the catalyst used for the alkylation reaction, maintaining the contents oi said alkylation zone under alkylation conditions, separating eiliuents of said alkylation zone into a liquid hydrocarbon phase and a liquid hydrofluoric acid phase, recovering from said hydrocarbon phase a hydrocarbon fraction comprising higher-boiling hydrocarbons produced by said alkylation, iractionally distilling at least a portion 01! said hydrofluoric acid phase to recover comprising said tempering agent together with hydrofluoric acid and undesired impurities, con

tacting said high-boiling fraction with a selective solvent for said tempering agent to remove said tempering agent therefrom, subsequently rccovering said tempering agent from said selective solvent and reintroducing said tempering agent into additional hydrofluoric acid charged to the process.

2. A process for alkylating a relatively lowboiling aikylatable hydrocarbon with a lowboiling olefin to produce higher-boiling hydrocarbons in the presence of concentrated hydrofluoric acid as a catalyst, which comprises admixing with liquid hydrofluoric acid between about 0.1 to 10 percent byweight of ammonia as a tempering agent, contacting the resultant liquid mixture with a hydrocarbon mixture containing a low-boiling olefin and saturated hydrocarbons to absorb said low-boiling olefin, introducing resulting liquid olefin-containing hydrofluoric acid cent by weight of ammonia as a tempering agent.

4. A process for aikylating a relatively lowboiling alkylatable hydrocarbon with a low-boiling. olefin to produce higher-boilin hydrocarbons in the presence of concentrated hydrofluoric acid as a catalyst, which comprises admixing with liquid hydrofluoric acid between about 0.1

to 10 per cent by weight of a polar organic nitrogen compound having a basic reaction as a tempering agent, contacting the resultant liquid mixture with a hydrocarbon mixture containing a low-boiling olefin and saturated hydrocarbons to absorb said low-boiling olefln, introducing resulting liquid olefin-containing hydrofluoric acid containing said tempering agent into an alkylation zone along with a. low-boiling alkylatabie hydrocarbon, maintaining the contents of said alkylation zone under alkylation conditions,

and recovering from efliuents of said alkylation zone a hydrocarbon fraction containing a higherboiling hydrocarbon produced by said alkylation.

5. An improved process for alkylating hydrocarbons, which comprises reacting under alkylation conditions a low-boiling alkylatable hydrocarbon and an olefin hydrocarbon in. the presence of liquid concentrated hydrofluoric acid associated with between about 0.1 and about 10 per cent by weight of quinoline as a tempering agent.

6. An improved process for alkylating hydro:- carbons, which comprises reacting under alkylation conditions a low-boiling alkylatable hydrocarbon and an olefin hydrocarbon in the presence of liquid concentrated hydrofluoric acid associated with between about 0.1 and about 10 percent by weight of an acid amide as a. tempering agent.

'7. An improved process for alkylating hydrocarbons, which comprises reacting under alkylation conditions a low-boiling alkylatable hydrocarbon and an olefin hydrocarbon in the presence of liquid concentrated hydrofluoric acid associated with between about 0.1 and about 10 per cent byweight of acetamide as a tempering agent.

8. The process of claim 4 wherein said polar organic nitrogen compound is ammonia.

9. A process for reacting isobutane with a lowboiling oiefln to produce higher-boiling paramnic hydrocarbons in the presence of concentrated hydrofiuoric acid as a catalyst, which comprises contacting a liquid mixture comprising liquid concentrated hydrofluoric acid associated with between about 0.1 and about 10 per cent by weight.

ingv agent is quinoline;

10. The process of claim 4 wherein said temper- 11. The process of claim a'wherein said tempwin agent is acetamide.

12. An improved process for alkylating hydro- \v carbons, which comprises reacting under alkylating conditions a low-boiling alkylatable hydrocarbon and an olefin hydrocarbon in the presence of liquid concentrated hydrofluoric acid associated with,, as a tempering agent, between about 0.1 and about 10 per cent by weight or a material selected from the class consisting of amino, amido, imino and imido compounds ammonia. qulnoiine, pyridine, and hexamethylene' tetra'mine. 1

RHEBENCES CHE The following references are of record in the file of this patent:

nm'rm STATES ra'rnn'i's Number Name Date 2,276,251 Morrell Mar. 10, 1942 2,317,694 Qtt Apr. 27, 1943 2,320,629 Matuszak June 1, 1943 

